KR20130034010A - Method for preparing a solid-state battery by sintering under pulsating current - Google Patents

Abstract

FIELD OF THE INVENTION The present invention relates to a method of providing a solid state lithium-ion battery having a solid state body, comprising: at least one powder mixing layer comprising a cathode active material and a solid electrolyte, at least one intermediate layer of a solid electrolyte, and a cathode The battery is assembled in a single process by stacking three or more layers at a pressure of at least 20 MPa through a pulsed current simultaneously with stacking one or more powder mixed layers comprising an activating material and a solid electrolyte. The present invention also relates to a lithium-ion battery obtained through the above method.

Description

METHODS FOR PREPARING A SOLID-STATE BATTERY BY SINTERING UNDER PULSATING CURRENT}

The present invention relates to a process for producing an "all-solid-state" lithium-ion battery by a pulse current sintering method and to an "all solid state" battery produced by the process.

The invention is applicable to the manufacture of "all solid" large capacity electrochemical generators (as opposed to micro batteries).

Micro-batteries are ultra-thin "all-solid-state" batteries in which each element of the battery is in the form of a thin solid layer (layered from ceramic material). It is generally composed of three or more layers, the layer consisting of a cathode (anode), an anode (cathode), and an electrode that separates the cathode and the anode and provides ion conductivity. In general, lithium metal is selected as the material of the negative electrode. The material used for the positive electrode is the same as that used for a conventional lithium-ion battery. Solid electrodes are generally glass oxide based materials, but oxysulfide or oxynitride may be used for better ionic conductivity.

Li-ion batteries are currently used in most mobile electronic devices on the market. Lithium-ion batteries have several advantages, in particular,

-No memory effect when compared with nickel-based capacitors,

-Low self-discharge,

-No management required,

-Has the advantage of having a high energy density per unit mass. Therefore, the battery is widely used in the field of mobile systems.

“All solid state” lithium-ion batteries, ie batteries in which two electrodes and electrolytes are made of a solid material, are drawing attention because they have better performance than conventional batteries based on liquid or gel electrolytes. This in particular provides a fundamental solution to the safety and environmental problems that have been a problem with conventional lithium-ion batteries. Rechargeable batteries without liquid electrolytes are, for example, thermally stable, free from leakage and contamination, have a strong resistance to shock and vibration, larger windows in electrochemical stability, and cells There is an advantage in the environmental impact of reprocessing.

The various layers of the microgenerator are mainly made by physical vapor phase deposition methods such as cathode sputtering and thermal evaporation. The layers are laid in succession, as a result of which the materials can be firmly bonded to each other and create a very fine contact surface. “All solid state” large capacity batteries consist of multiple layers of composite / electrolyte / Li—M metal alloy electrodes, in which the bonding between the layers is usually achieved through a simple cooling pressure method. Kitaura H. et al., " Journal of Power Sources , 2009, 189 , 145-148," describes a method for producing a "all-solid" Li-In / Li ₄ Ti ₅ O ₁₂ battery, wherein the electrolyte of the battery It is made by crystallizing the ceramic and then the electrode and electrolyte are combined by cooling pressure method. In Sakuda A. et al., " Journal of Power Sources , 2009, 189 , 527-530", furthermore, oxide coated (Li ₂ SiO ₃ and SiO ₂ ) LiCoO ₂ electrodes and ceramic electrolytes (Li ₂ SP ₂ S ₅ ) The manufacturing method of the lithium secondary battery containing is described. In the method described in this document, the ceramic electrolyte layer is produced independently by heat treatment (for 4 hours at 210 ° C.). The anode is made using a mixture of LiCoO ₂ powder and ground ceramic electrolyte. The cathode is indium foil. However, as a second embodiment, the step of generating the battery requires a plurality of steps and limited conditions, which is achieved by cold compressing the anode layer and the ceramic electrolyte and then applying the indium foil to the argon air in the glove box. Because it is formed. In addition, the technique of forming the battery by the cooling pressure method does not guarantee a good interface between the layers, so there are many mechanical limitations, which means that thin electrodes must be used and these electrodes are very thin. This means that the electrode contains less active material (7 mg per range of 0.97 cm ² , ie less than 9 mg / cm ² active material).

In addition, a method of producing a thin (electrode and / or solid electrolyte) film through pulsed current sintering has been conventionally presented. In Xu X. et al., "Material Research Bulletin, 2008, 43 , 2334-2341," NASICON-type structure through pulse current sintering of Li _1.4 Al _0.4 Ti _1.6 (PO ₄ ) ₃ (LATP) nanopowder. A method for producing a solid electrolyte having a (structure of the mixture Na ₃ Zr ₂ Si ₂ PO ₁₂ ) is described.

Nagata K. et al., " Journal of Power Sources , 2007, 174 , 832-837", describes a method for producing a "all solid state" ceramic battery by a sintering method. The manufacture of "all-solid-state" batteries comprising solid crystalline oxide electrolytes in this document indicates that heat treatment causes a solid state reaction between the electrolyte layer and the active electrode material in contact with the electrolyte layer, The manufacture of batteries is described as difficult in that the electrochemical deactivation state of the interface of the electrolyte / electrode is caused. The authors of this document used phosphates such as Li _1.3 Al _0.3 Ti _1.7 (PO ₄ ) ₃ (LATP) as solid electrolytes and phosphates such as LiCoPO ₄ et Li ₃ Fe ₂ (PO ₄ ) ₃ as active electrode materials. This does not cause a chemical reaction and can carry out co-sintering, after which the interface becomes active. In this case, the sintering operation is performed for 5 hours at 800 ℃ in air. However, the electrode material used according to the process of this document does not have an electron-conductivity to provide an agent, unlike the electrode material, which is very small electrode thickness (10 μm) to produce a battery having advantageous electrochemical properties. But its capacity is similar to that of a micro-battery.

Finally, document EP 2 086 038 describes an all-solid-state battery comprising a positive electrode, a negative electrode and a solid electrolyte disposed between the two electrodes. Each electrode comprises an active material (eg LiMn ₂ O _{4 at the} positive electrode or SiO _{2 at the} negative electrode) and includes an ion conductive agent (electrolyte) and an electron conductive agent such as carbon or graphite. The content of the electrolyte does not exceed 30 wt% with respect to the weight of the electrolyte. In particular, this document states that if the content of the electrolyte and the content of the electron-conducting generator are too high, the amount of active material in each electrode will be reduced and consequently the capacity of the battery will be reduced. It is. In addition, the electrode layer obtained here has a thickness as thin as about 12-15 μm. However, the thin thickness may reduce the amount of energy that can be stored in the battery. This document also describes a method of manufacturing the battery. The process consists of a plurality of steps, each of which comprises producing a positive electrode strip, manufacturing a negative electrode strip, and producing an intermediate electrode strip, respectively. To this end, an acrylic binder (polymer) is used for each strip, which is then incinerated and subsequently removed. Thereafter, the electrode strip is pressed against the electrolyte strip and the assembly is sintered.

Thus, to date, all-solid-state lithium-ion battery manufacturing methods having good electrochemical properties and having thin ceramic electrodes (eg, thicknesses of about 30 μm or less), in particular electron-conducting generators in composite electrodes, There is no battery manufacturing method obtained in a single process in this regard, and the conventional method has an adverse effect on the density of the electrode and the adhesion at the electrode / electrolyte interface in the composite electrode.

Therefore, the inventor of the present invention has an object to provide a battery manufacturing method that solves the above problems.

One of the subjects of the present invention has a monolithic body comprising at least one composite cathode layer and at least one composite anode layer, the layers separated from each other by at least one intermediate solid electrolyte layer, all- solid-state) lithium-ion battery manufacturing method,

Preparing a powdery mixture (MP1) comprising at least one active cathode material powder, at least one solid electrolyte powder and at least one electron-conductive generating agent; And

Preparing a powdered mixture (MP2) comprising at least one active lithium-based positive electrode material powder, at least one solid electrolyte powder and at least one electron-conductive generating agent;

The battery is formed in a single process by superimposing at least one mixture (MP1) layer and at least one mixture (MP2) layer, the layers being separated from each other by one or more solid intermediate electrolyte layers in powder form The layers are sintered using a pulse current at a pressure of 20 MPa or more in a set,

The particle size of the solid electrolyte in powder form is 5 μm or less,

The contents of the solid electrolyte of each of the mixture (MP1) and the mixture (MP2) are independently of each other in the range of 10 to 80 wt%,

The content of the electron-conducting generating agent of each of the mixture (MP1) and the mixture (MP2) is independently from each other in the range of 2 to 25 wt%,

The content of the active electrode material of each of the mixture (MP1) and the mixture (MP2) relates to a process for producing a lithium-ion battery, characterized in that it is in the range of 20 to 85 wt% independently of one another.

According to the method, the presence of a solid electrolyte in each of the three layers forming a battery results in a homogeneous chemical mixture, which causes several components to become dense at the same temperature at the same temperature, especially at the interface of the electrode / electrolyte and Li ⁺ − It means that the conductive grating is continuous between one composite electrode and the other composite electrode. In addition, since each of the three layers of the multi-layer contains an electrolyte, the stress created by connecting materials having different coefficients of thermal expansion are absorbed, thereby causing a blocking phenomenon of the rate of change of the concentrated state.

Compared with the conventional method, the method according to the present invention has the following advantages.

The present invention makes it possible to make "all solid" lithium-ion batteries with ceramic electrodes in a single process.

Since the present invention sinters three layers simultaneously at a single temperature, the parasitic chemistry at the different temperatures is a multiple process using different temperatures which leads to a parasitic chemical reaction which has previously limited the use of a plurality of layers. Unlike the prior art, which caused the reaction to limit the use of a plurality of layers in the past, it can be implemented quickly and simply, and there is no need for preliminary work (green paper, etc.) other than mixing powder of the composite electrode.

At the same time a good contact state at the electrode / electrolyte interface is ensured, while no parasitic reactions occur between the components of the various layers of the battery, in particular between the electron-conducting generator and the other electrode components.

The present invention can produce a self-supporting battery that does not require a substrate.

The present invention can produce a battery having a composite electrode having good electron-conducting properties and having a thickness significantly larger than that of a "all solid state" lithium-ion battery, said "all solid state" lithium-ion battery Does not include an electron-conducting generator.

The present invention makes it possible to produce "all solid" lithium-ion batteries in which the electrode layers in the battery can now be technically realized, in particular batteries which are thicker than those in which each electrode layer in the battery has a thickness of at least 30 μm. As a result, a battery with a significantly larger storage capacity can be manufactured.

The present invention can produce a battery that is more thermally stable than conventional lithium-ion batteries in both charged and discharged states. Such batteries can operate at higher temperatures (> 130 ° C. and 350 ° C. or less) than conventional batteries.

Preferably, the particle size of the solid electrolyte powder that can be used in the mixture (MP1), the mixture (MP2) and the intermediate electrolyte layer is the particle size of the other powdered components present in the mixture (MP1) and the mixture (MP2). Is less than According to a particularly preferred embodiment of the invention, the particle size of the solid electrolyte powder is 1 μm or less. In this case, it is preferably 0.1 to 1 m.

The average particle size of the mixture (MP1) and the mixture (MP2) is larger than the average particle size of the solid-electrolyte powder. Preferably, the average particle size of the mixture (MP1) and the mixture (MP2) is independently in the range of 1 to 10 mu m, more preferably in the range of 1 to 3 mu m.

According to a preferred embodiment of the present invention, the particle size of the mixture MP1 is substantially the same as the particle size of the mixture MP2. In the present invention, "substantially the same particle size" means that the maximum particle size difference between the mixture (MP1) and the mixture (MP2) is ± 2 μm.

The active negative electrode material may be selected from lithium phosphate, titanium oxide / lithium such as Li ₄ Ti ₅ O ₁₂ , niobium phosphate such as PNb ₉ O ₂₅ , silicon and graphite.

Of the lithium phosphates that can be used as the active cathode material, Li ₃ V ₂ (PO ₄ ) ₃ , LiTi ₂ (PO ₄ ) ₃ , or mixtures thereof are most preferred.

The mixtures recommended as active cathode materials (Li ₃ V ₂ (PO ₄ ) ³ , LiTi ₂ (PO ₄ ) ³ , PNb ₉ O _25, Li ₄ Ti ₅ O ₁₂ ) are AlPO ₄ , Li ₂ SiO ₃ , ZrO ₂ It may be coated with a protective layer, such as FePO ₄ .

Solid electrolytes which can be used according to the invention are preferably lithium having the general formula Li _{1 + x} Al _x M _2-x (PO ₄ ) ₃ when M = Ge, Ti, Zr, Hf and 0 <x <1 Selected from phosphates. Of the lithium phosphates the mixtures Li _1.5 Al _0.5 Ge _1.5 (PO ₄ ) ₃ and Li _1.3 Al _0.3 Ti _1.7 (PO ₄ ) ₃ are particularly preferred.

According to a first embodiment of the invention, the three layers forming a battery comprise the same electrode.

In the present invention, "same electrode" means that the electrode's chemical properties and particle size are the same in the mixture (MP1), the mixture (MP2) and the intermediate electrolyte layer.

According to a second embodiment of the present invention, the solid electrolyte present in the mixture MP1 is different from the solid electrolyte present in the mixture MP2.

In the present invention, "different electrolytes" have the meaning including both different chemical properties and different physical properties such as different particle sizes.

If the solid electrolyte present in the mixture MP1 is different from the solid electrolyte present in the mixture MP2, the mixture (MP1) layer comprises at least one solid electrolyte (E1) and the mixture (MP2) layer is the solid An electrolyte layer comprising at least one solid electrolyte (E2) different from the electrolyte (E1) and separating the mixture (MP1) layer and the mixture (MP2) layer comprises at least one electrolyte (which is in contact with the mixture (MP1) layer). E1) layer, and at least one electrolyte (E2) layer in contact with the mixture (MP2) layer.

According to a preferred embodiment, the solid electrolyte content of each of the mixtures is from 10 to 80 wt%. The content can vary between the mixture MP1 and the mixture MP2 and depends on the electron and ion conducting properties of the active material. According to a more preferred embodiment, the solid electrolyte content of each of the mixture (MP1) and the mixture (MP2) is independently of each other in the range of 30 to 80 wt%, in particular 35 to 80 wt%, more preferably more than 30 and less than 80 wt% Is in.

The active anode material is preferably selected from lithium phosphate and lithium oxide. Among the lithium phosphates that can be used as the active cathode material, materials, LiFePO ₄ , LiCoPO ₄ , LiNiPO ₄ , LiMnPO ₄ , Li ₃ V ₂ (PO ₄ ) ₃ , Li ₃ Fe ₂ (PO ₄ ) ₃ are most preferred. Of lithium oxides (when X = Co, Ni, Mn, or a combination thereof) LiXO ₂ is preferred, and mixtures thereof can be used.

These various compounds, which are recommended as the active anode material, can be coated with a protective layer such as AlPO ₄ , Li ₂ SiO ₃ , ZrO ₂ , FePO ₄ .

According to the invention, the content of the active electrode material of each of the mixture MP1 and the mixture MP2 is independently of each other in the range of 20 to 85 wt%.

According to a preferred embodiment of the present invention, the active cathode material, at least one solid electrolyte, and active cathode material are selected from lithium phosphate.

Preferably, in the method of manufacturing the “all solid state” lithium-ion battery, the active positive electrode material will be different from the active negative electrode material.

Electron-conducting generators are carbon-based materials (powders, fibers, nanotubes, etc.), and metals such as Ni, Cu, Al (these metals are selected according to operating potential, Cu is suitable for the cathode and Al is suitable for the anode). And metal nitrides such as TiN.

According to a preferred embodiment of the present invention, the electron-conducting generating agent is a carbon-based material in the form of particles having a nano unit size.

According to the invention, the content of the electron-conducting generating agent is in the range of 2 to 25 wt%. The content can vary between the mixture (MP1) and the mixture (MP2) and depends on the particle size and the electron-conducting nature of the active material.

The sintering action is preferably carried out in a primary or secondary vacuum environment in an argon or nitrogen atmosphere.

The pressure exerted on the layer during the sintering action can vary. According to a preferred embodiment of the invention, the sintering action is carried out at a pressure of 5 to 200 MPa, more preferably at a pressure of about 100 MPa.

The maximum sintering temperature is in the range of 500 to 1000 ° C.

The duration of the sintering action varies with temperature. This period is generally in the range of 1 to 60 minutes.

According to a preferred embodiment of the present invention, the sintering action is carried out under a secondary vacuum environment having a maximum sintering temperature of 600 to 700 ° C. and a pressure of about 100 MPa for 2 to 4 minutes. The total heat treatment time is at least 15 minutes in this case.

The sintering temperature can be reached via a gradual temperature stabilizer by applying a pulsed current for several cycles.

The magnitude of the pulse current is in the range of 10 to 8000 A. Each pulse is approximately a few ms long. Preferably the length is 1 to 5 ms.

Further refinement of the method according to the invention provides that at least one current collector and / or the outer surface of the mixture (MP1) layer and / or so that the mixture (MP1) layer, the electrolyte layer and the mixture (MP2) layer are sintered simultaneously during battery formation. Or on the outer surface of the mixture (MP2) layer. By "outer surface" of the mixture (MP1) and mixture (MP2) layers is meant the surface of the mixture (MP1) layer and / or the mixture (MP2) layer that is not in contact with the intermediate solid electrolyte layer.

The current collector generally has a powder form, a network form, and one or more foil forms.

The current collector is selected from copper, nickel, stainless steel, aluminum, carbon, titanium, silver, gold, platinum, or alloys thereof.

The materials are selected according to the operating potentials of the active materials of the anode and cathode. These materials do not necessarily oxidize or diminish when in contact with the electrode material. As such, copper is preferred for low potential materials while aluminum is preferred for high potential materials.

In general, in order to simultaneously sinter five or more layers of the first collector / mixture (MP1) layer / solid electrolyte layer / mixture (MP2) layer / second collector, the first current collector is the outer surface of the mixture (MP1) layer. And a second current collector is located on the outer surface of the mixture (MP2) layer.

The invention also relates to a "all solid state" lithium-ion battery obtained by carrying out the production process according to the invention, the battery comprising a monolithic body formed by three or more overlapping layers,

At least one composite anode layer comprises at least one active cathode material, at least one solid electrolyte, and at least one electron-conducting generator,

At least one composite anode layer comprises at least one active lithium-based anode material, at least one solid electrolyte, and at least one electron-conducting generator,

At least one intermediate solid electrolyte layer separates the composite cathode layer and the composite anode layer,

The content of the solid electrolyte in each of the composite electrode layers is in the range of 10 to 80 wt%, independently of each other,

The content of the electron-conducting generating agent of each of the composite electrode layers is independently in the range of 2 to 25 wt%;

-In a lithium-ion battery, characterized in that the contents of the active cathode and anode materials of each of the composite electrode layers are independently of each other in the range of 20 to 85 wt%.

The thickness of each of the composite electrode layers is independently of one another in the range of 30 to 1400 μm.

The solid electrolyte content of each of the composite electrode layers is independently of each other in the range of 30 wt% to 80 wt%, preferably 35 wt% to 80 wt%, more preferably more than 35 wt% to less than 80 wt%.

According to the invention, the thickness of each of the electrode layers is independently from each other in the range of about 30 to 800 μm, preferably 50 to 800 μm, more preferably 50 to 500 μm.

The thickness of the intermediate electrolyte layer is in the range of about 10 to 500 μm, preferably about 10 to 60 μm.

According to a further improved invention, the monolithic body further comprises at least one current collector superimposed on the composite cathode layer and / or the composite anode layer on the outer surface.

Preferably, the current collector layer is selected from copper, nickel, stainless steel, aluminum, carbon, titanium, silver, gold, platinum, or alloys thereof.

The invention is also a battery stack (multi-cell pack) comprising two or more batteries as described above, wherein the two or more batteries are connected via a current collector belonging to one of the batteries. According to the present invention, "physical barrier to prevent ion migration" means that the current collector has a sintered powder or foil form but no reticulated form that does not form a physical barrier to prevent ion migration.

As such, regardless of whether the electrode is positive or negative, the current collector connects two batteries at one of the electrodes of the battery. This is because the current collector is simultaneously compatible with all of the electrodes to which the current collector is connected. Furthermore, the current collector can connect two cathodes or two anodes. In this case, it means that the batteries are connected in series with each other. In addition, the current collector may be connected to the cathode and the anode. In this case, the battery may be said to be connected in series (bipolar structure).

It is also possible to superimpose two current collectors (each current collector belonging to each battery) (optionally through the alloy located between the two current collectors and corresponding electrode potentials) at the junction between the two batteries. have.

The objects, configurations and effects of the present invention will be explained in more detail through the following detailed description and exemplary embodiments.

Example

Several inorganic materials used in this example but not commercially available were previously synthesized using methods known in the literature:

Lithium iron phosphate (LiFePO ₄ ): Delacourt, C. et al. , Solid State Ionics , 2004, 173 , 113-118;

Lithium aluminum germanium phosphate (Li _1.5 Al _0.5 Ge _1.5 (PO ₄ ) ₃ ): M. Cretin, P. Fabry, J Eur. Ceram. Soc. , 1999, 19 , 2931-2940; And

Lithium vanadium phosphate (Li ₃ V ₂ (PO ₄ ) ₃ ): S. Patoux et al , J. Power Sources , 2003, 119-121 , 278-284.

Example 1 Fabrication of "all-solid-state" Li-ion batteries according to the method of the invention

In this example, a 15 mm-diameter battery was produced, wherein the anode / cathode mass ratio was determined in an electrode composition comprising 25 wt% active electrode material, 60 wt% electrolyte, and 15 wt% electron-conductive generating agent. About 1.2.

The battery consisted of:

0.0215 g of LiFePO ₄ (LFP) with an average particle size of 15-20 μm, 0.0515 g of Li _1.5 Al _0.5 Ge _1.5 (PO ₄ ) ₃ (LAG) with an average particle size of 5-10 μm, and an average particle size A cathode consisting of 0.0219 g of carbon black, 50-100 nm and sold under the name Super P? By Timcal. The mixture of ingredients was manually milled in agate mortar for 20 minutes;

0.0178 g of Li ₃ V (PO ₄ ) ₃ (LVP) with an average particle size of 30-40 μm, 0.0426 g of LAG with an average particle size of 5-10 μm, and an average particle size of 50-100 nm and Timcal 0.0106 g of Super P? Cathode consisting of carbon. The mixture of ingredients was manually ground in agate induction for 20 minutes; And

A solid electrolyte consisting of 0.2412 g of Li _1.5 Al _0.5 Ge _1.5 (PO ₄ ) ₃ with a particle size of 0.4 to 5 μm.

Thereafter, the various mixtures comprising the anode, electrolyte and cathode were continuously placed in a 15 mm-diameter graphite die (grade 2333, Carbone Lorraine), the inside being a flexible graphite film sold under the name Papyex® by Carbone Lorraine. Protected. The die was then closed by a symmetrical piston, also made of grade 2333 graphite, introduced into a chamber of an SPS instrument sold under the name Dr Sinter 2080® by Sumitomo Inc., after which the chamber was pumped into secondary vacuum. The battery was then formed by applying two lamps, a pressure lamp and a temperature lamp. A pressure of 100 Mpa was achieved within 3 minutes and maintained for the rest of the synthesis (7 minutes). A temperature of 650 ° C. was achieved in two steps: a lamp of 100 ° C. min ⁻¹ for 5 minutes, then a lamp of 50 ° C. min ⁻¹ for 3 minutes. Thereafter, the temperature was maintained for 2 minutes. The temperature ramp was obtained by applying a finite pulse DC current over 14 cycles of 3.2 ms (12 cycles of pulse and 2 cycles without pulse). The die was then cooled in the chamber of the SPS. The battery thus obtained was wiped with sandpaper, leaving the remaining Papyex? The film was removed.

Thus, a monolithic 15 mm-diameter Li-ion battery having a total thickness of 870 μm was obtained, which comprises a 220 μm-thick composite anode layer, a 430 μm-thick intermediate solid-electrolyte layer and a negative electrode material. Consists of a 220 μm-thick layer.

In the battery, the anode / cathode mass ratio was 25 wt% active electrode material, 60 wt% Li _1.5 Al _0.5 Ge _1.5 (PO ₄ ) ₃ electrolyte, and 15 wt% Super P? 1.2 for electrode compositions comprising carbon.

1 attached to the present specification includes a) an all-solid-state battery thus obtained, b) a cross-sectional image of a battery with three overlapping layers visible, and c) a backscatter-electron scanning electron microscope of the same cross-section ( SEM) pictures are shown.

Example 2 Preparation of "All Solid" Li-Ion Batteries According to the Method of the Invention

In this example, an 8 mm-diameter battery was produced, where the anode / cathode mass ratio was 0.72 for an electrode composition comprising 25 wt% active electrode material, 60 wt% electrolyte and 15 wt% electron-conducting generator.

The battery consisted of:

0.0115 g of LFP with an average particle size of 15-20 μm, 0.0276 g of LAG with an average particle size of 5-10 μm, and 0.0069 sold by Timcal under the product name Super P? Anode consisting of g carbon black. The mixture of ingredients was manually ground in agate induction for 20 minutes;

0.016 g LVP with an average particle size of 30-40 μm, 0.0384 g of LAG with an average particle size of 5-10 μm, and 0.0096 g of Super P commercially available from Timcal with an average particle size of 50-100 nm. Cathode consisting of carbon. The mixture of ingredients was manually ground in agate induction for 20 minutes; And

A solid electrolyte consisting of 0.078 g of LAG with an average particle size of 5-10 μm.

Thereafter, the various mixtures comprising the positive electrode, the electrolyte and the negative electrode were continuously placed in an 8 mm-diameter graphite die (grade 2333, Carbone Lorraine), the inside of which was Papyex®. Protected with film. The die was then closed by a symmetric piston also made of grade 2333 graphite and introduced into the chamber of the SPS instrument used in Example 1, after which the chamber was pumped into secondary vacuum. The battery was then formed under the conditions described in Example 1 above.

An 8 mm-diameter “full solid state” battery with a total thickness of 1600 μm was obtained, which was made up of a 400 μm-thick composite anode layer, a 500 μm-thick intermediate solid-electrolyte layer, and a 714 μm-thick layer of negative electrode material. It is composed.

Then, an electrochemical test was performed on the battery. To perform the electrochemical test, hundreds of nanometer gold layers were deposited on two sides of the battery by cathode deposition.

After that, the battery is Swagelok? It was placed in the cell and assembled in an inert atmosphere glove box. Subsequently, the battery is a Solartron 1470? The test system was tested in constant current mode. To perform the FIG. Test, the cell was placed in a climatic chamber, which was operated at a temperature of 25 ° C to 150 ° C. This state is indicated by C / n, which corresponds to a full charge or discharge of the battery within n hours.

2 attached to this specification shows cycling obtained at 140 ° C. (2 cycles, off-white curve) and 120 ° C. (6 cycles, black curve) in the same cycling state of C / 20 (ie, full charge and discharge within 20 hours). The curve is shown. In FIG. 2, the potential V (Li ⁺ / Li) is a function of the amount of lithium inserted per mole of active material at the cathode.

This curve shows that i) all effective capacities are recovered, ii) the good circulation of the battery.

Example 3 Preparation of "All Solid" Li-Ion Batteries According to the Method of the Invention

In this example, an 8 mm-diameter battery was produced, where the anode / cathode mass ratio was 1.00 for an electrode composition comprising 25 wt% active electrode material, 60 wt% electrolyte and 15 wt% electron-conducting generator.

The battery consisted of:

Anode and cathode, where both anode and cathode are 0.0081 g of LVP with an average particle size of 30-40 μm, 0.0195 g of LAG with an average particle size of 5-10 μm, and an average particle size of 50-100 nm and Timcal Consists of 0.0049 g of carbon black sold under the name Super P? By the company. The mixture of ingredients was manually ground in agate induction for 20 minutes; And

A solid electrolyte consisting of 0.078 g of LAG with an average particle size of 5-10 μm.

The various mixtures comprising the anode, electrolyte and cathode were then placed successively in an 8 mm-diameter graphite die (grade 2333, Carbone Lorraine), inside a flexible graphite film sold under the name Papyex® by Carbone Lorraine. Protected. The die was then closed by a symmetrical piston, also made of grade 2333 graphite, introduced into a chamber of an SPS instrument sold under the name Dr Sinter 2080® by Sumitomo Inc., after which the chamber was pumped into secondary vacuum. The battery was then formed by applying two lamps, a pressure lamp and a temperature lamp. A pressure of 100 Mpa was achieved within 3 minutes and maintained for the rest of the synthesis (7 minutes). A temperature of 680 ° C. was achieved in two steps: a lamp of 100 ° C. min ⁻¹ for 6 minutes, followed by a lamp of 40 ° C. min ⁻¹ for 2 minutes. Thereafter, the temperature was maintained for 2 minutes. The temperature ramp was obtained by applying a finite pulse DC current over 14 cycles of 3.2 ms (12 cycles of pulse and 2 cycles without pulse). The die was then cooled in the chamber of the SPS. The battery thus obtained was wiped with sandpaper, leaving the remaining Papyex? The film was removed.

An 8 mm-diameter “all solid state” battery with a total thickness of 1000 μm was obtained, which had a 250 μm-thick composite anode layer, a 500 μm-thick intermediate solid-electrolyte layer and a 250 μm-thick layer of negative electrode material. It consists of.

In the battery, the anode / cathode mass ratio is 25 wt% Li ₃ V ₂ (PO ₄ ) ₃ active electrode material, 65 wt% Li _1.5 Al _0.5 Ge _1.5 (PO ₄ ) ₃ electrolyte and 15 wt% Super P? 1 for the electrode composition comprising carbon.

Thereafter, the electrochemical test described in Example 2 was performed on the battery.

3 attached to this specification shows 100 ° C. (1 cycle for C / 40: gray white curve), 110 ° C. (3 cycles for C / 20: black curve) and finally 120 ° C. (3 cycles for C / 20). The cycling curve obtained in the dashed line curve is shown. In FIG. 3, the potential V (Li ⁺ / Li) is a function of the capacity (mAh / g) and the amount of lithium inserted per mole of active material.

This curve shows that the battery's circulation is very good and the increase in temperature improves the performance obtained.

4 attached to this specification shows the change in specific capacity of the battery for various conditions and various temperatures.

In Fig. 4, the capacity of the battery (mAh / g) is a function of the number of cycles, the empty triangle corresponds to the charging capacity (mAh / g), and the solid triangle corresponds to the discharge capacity (mAh / g).

Example 4 Preparation of "All Solid" Li-Ion Batteries According to the Method of the Invention

In this example, an 8 mm-diameter battery was produced, where the anode / cathode mass ratio was 0.5 for an electrode composition comprising 25 wt% active electrode material, 60 wt% electrolyte and 15 wt% electron-conductive generating agent.

The battery consisted of:

0.0125 g of LVP with an average particle size of 30-40 μm, 0.03 g of LAG with an average particle size of 5-10 μm, and 0.0075 sold by Timcal under the product name Super P? Anode consisting of g carbon black. The mixture of ingredients was manually ground in agate induction for 20 minutes;

0.025 g of LVP with an average particle size of 30-40 μm, 0.06 g of LAG with an average particle size of 5-10 μm, and 0.015 sold by Timcal under the product name Super P? A negative electrode composed of g carbon black. The mixture of ingredients was manually ground in agate induction for 20 minutes; And

A solid electrolyte consisting of 0.074 g of LAG with an average particle size of 5-10 μm.

The various mixtures comprising the anode, electrolyte and cathode were then placed successively in an 8 mm-diameter graphite die (grade 2333, Carbone Lorraine), inside a flexible graphite film sold under the name Papyex® by Carbone Lorraine. Protected. The die was then closed by a symmetrical piston, also made of grade 2333 graphite, introduced into a chamber of an SPS instrument sold under the name Dr Sinter 2080® by Sumitomo Inc., after which the chamber was pumped into secondary vacuum. The battery was then formed by applying two lamps, a pressure lamp and a temperature lamp. A pressure of 100 Mpa was achieved within 3 minutes and maintained for the rest of the synthesis (7 minutes). A temperature of 680 ° C. was achieved in two steps: a lamp of 100 ° C. min ⁻¹ for 6 minutes, followed by a lamp of 40 ° C. min ⁻¹ for 2 minutes. Thereafter, the temperature was maintained for 2 minutes. The temperature ramp was obtained by applying a finite pulse DC current over 14 cycles of 3.2 ms (12 cycles of pulse and 2 cycles without pulse). The die was then cooled in the chamber of the SPS. The battery thus obtained was wiped with sandpaper, leaving the remaining Papyex? The film was removed.

An 8 mm-diameter “full solid state” battery with a total thickness of 1630 μm was obtained, which consisted of a 380 μm-thick composite anode layer, a 500 μm-thick intermediate solid-electrolyte layer and a 750 μm-thick layer of negative electrode material. It is composed.

In the battery, the anode / cathode mass ratio is 25 wt% Li ₃ V ₂ (PO ₄ ) ₃ active electrode material, 65 wt% Li _1.5 Al _0.5 Ge _1.5 (PO ₄ ) ₃ electrolyte and 15 wt% Super P? 0.5 for an electrode composition comprising carbon.

Thereafter, the electrochemical test described in Example 2 was performed on the battery.

5 attached to this specification shows the electrochemical curves for the battery obtained at various states and at various potential windows (1-2.2 V and 1-2.4 V). In FIG. 5, the potential V (Li ⁺ / Li) is a function of the capacity (mAh / g) and the amount of lithium inserted per mole of active material at the cathode: black curve at 120 ° C. (C / 20 at 1 to 2.2 V). Corresponds to cycling performed in 1 cycle); The off-white curve corresponds to cycling performed at 120 ° C. (3 cycles for C / 10 at 1-2.2 V); Finally, the black cross line corresponds to the cycling performed at 120 ° C. (1 cycle for C / 20 at 1 to 2.4 V).

Example 5 Preparation of "All Solid" Li-Ion Batteries According to the Method of the Invention

In this example, an 8 mm-diameter battery was produced, where the anode / cathode mass ratio was 1.0 for an electrode composition comprising 42.5 wt% active electrode material, 42.5 wt% electrolyte, and 15 wt% electron-conductive generating agent.

The battery consisted of:

Anode and cathode where both anode and cathode are 0.021 g LVP with an average particle size of 30-40 μm, 0.021 g LAG with an average particle size of 5-10 μm, and an average particle size of 50-100 nm and Timcal Consists of 0.0075 g of carbon black sold under the name Super P? By the company. The mixture of ingredients was manually ground in agate induction for 20 minutes; And

A solid electrolyte consisting of 0.06 g of LAG with an average particle size of 5-10 μm.

The various mixtures comprising the anode, electrolyte and cathode were then placed successively in an 8 mm-diameter graphite die (grade 2333, Carbone Lorraine), inside a flexible graphite film sold under the name Papyex® by Carbone Lorraine. Protected. The die was then closed by a symmetrical piston, also made of grade 2333 graphite, introduced into a chamber of an SPS instrument sold under the name Dr Sinter 2080® by Sumitomo Inc., after which the chamber was pumped into secondary vacuum. The battery was then formed by applying two lamps, a pressure lamp and a temperature lamp. A pressure of 100 Mpa was achieved within 3 minutes and maintained for the rest of the synthesis (7 minutes). A temperature of 680 ° C. was achieved in two steps: a lamp of 100 ° C. min ⁻¹ for 6 minutes, followed by a lamp of 40 ° C. min ⁻¹ for 2 minutes. Thereafter, the temperature was maintained for 2 minutes. The temperature ramp was obtained by applying a finite pulse DC current over 14 cycles of 3.2 ms (12 cycles of pulse and 2 cycles without pulse). The die was then cooled in the chamber of the SPS. The battery thus obtained was wiped with sandpaper, leaving the remaining Papyex? The film was removed.

An 8 mm-diameter “all solid state” battery with a total thickness of 1240 μm was obtained, which was made up of a 415 μm-thick composite anode layer, a 410 μm-thick intermediate solid-electrolyte layer, and a 415 μm-thick layer of negative electrode material. It is composed.

In the battery, the anode / cathode mass ratio was 42.5 wt% Li ₃ V ₂ (PO ₄ ) ₃ active electrode material, 42.5 wt% Li _1.5 Al _0.5 Ge _1.5 (PO ₄ ) ₃ electrolyte, and 15 wt% Super P? 1 for the electrode composition comprising carbon.

Thereafter, the electrochemical test described in Example 2 was performed on the battery.

6 attached to the specification shows the electrochemical curves for the battery obtained at 120 ° C. and various states. In FIG. 6, the potential V is a function of the amount of lithium inserted per mole of active material (grey line: cycle for C / 32; black line: cycle for C / 20).

Example 6 Preparation of "All Solid" Li-Ion Batteries According to the Method of the Invention

In this example, an 8 mm-diameter battery was produced, where the anode / cathode mass ratio was 1 for an electrode composition comprising 25 wt% active electrode material, 60 wt% electrolyte and 15 wt% electron-conducting generator.

The battery consisted of:

0.05 g of LiCoPO ₄ (LCP) with an average particle size of 1 μm, 0.12 g of Li _1.5 Al _0.5 Ge _1.5 (PO ₄ ) ₃ (LAG) with an average particle size of 5-10 μm, and an average particle size of 50 Anode consisting of 0.03 g of carbon black sold at -100 nm and sold under the name Super P® by Timcal. The mixture of ingredients was manually ground in agate induction for 20 minutes;

0.05 g of Li ₃ V (PO ₄ ) ₃ (LVP) with an average particle size of 30-40 μm, 0.12 g of LAG with an average particle size of 5-10 μm, and an average particle size of 50-100 nm and Timcal 0.03 g of Super P? Cathode consisting of carbon. The mixture of ingredients was manually ground in agate induction for 20 minutes; And

A solid electrolyte consisting of 0.1 g of Li _1.5 Al _0.5 Ge _1.5 (PO ₄ ) ₃ with a particle size of 0.4 to 5 μm.

The various mixtures comprising the anode, electrolyte and cathode were then placed successively in an 8 mm-diameter graphite die (grade 2333, Carbone Lorraine), inside a flexible graphite film sold under the name Papyex® by Carbone Lorraine. Protected. The die was then closed by a symmetrical piston, also made of grade 2333 graphite, introduced into a chamber of an SPS instrument sold under the name Dr Sinter 2080® by Sumitomo Inc., after which the chamber was pumped into secondary vacuum. The battery was then formed by applying two lamps, a pressure lamp and a temperature lamp. A pressure of 100 Mpa was achieved within 3 minutes and maintained for the rest of the synthesis (7 minutes). A temperature of 650 ° C. was achieved in two steps: a lamp of 100 ° C. min ⁻¹ for 5 minutes, then a lamp of 50 ° C. min ⁻¹ for 3 minutes. Thereafter, the temperature was maintained for 2 minutes. The temperature ramp was obtained by applying a finite pulse DC current over 14 cycles of 3.2 ms (12 cycles of pulse and 2 cycles without pulse). The die was then cooled in the chamber of the SPS. The battery thus obtained was wiped with sandpaper, leaving the remaining Papyex? The film was removed.

A monolithic 8 mm-diameter Li-ion battery with a total thickness of 3030 μm was obtained, which consisted of a 940 μm-thick composite anode layer, a 740 μm-thick intermediate solid-electrolyte layer and a 1350 μm-thick layer of negative electrode material. It is composed.

In the battery, the anode / cathode mass ratio was 25 wt% active electrode material, 60 wt% Li _1.5 Al _0.5 Ge _1.5 (PO ₄ ) ₃ electrolyte, and 15 wt% Super P? 1 for the electrode composition comprising carbon.

Example 7 Preparation of "All Solid" Li-Ion Cells According to the Method of the Invention

In this example, an 8 mm-diameter battery stack was fabricated, wherein the anode / cathode mass ratio was determined in an electrode composition comprising 25 wt% active electrode material, 60 wt% electrolyte and 15 wt% electron-conducting generator. About 0.5.

7 attached hereto is a schematic diagram of a cell 1 comprising two batteries connected in parallel.

In the order shown in FIG. 7 the cell 1 consists of:

A 20 μm (copper foil) current collector 2;

0.0125 g of LVP with an average particle size of 30-40 μm, 0.03 g of LAG with an average particle size of 5-10 μm, and 0.0075 g of Super P commercially available from Timcal with an average particle size of 50-100 nm. First cathode (3) consisting of carbon. The mixture of ingredients was manually ground in agate induction for 20 minutes;

A solid electrolyte 4 composed of 0.03 g of LAG with an average particle size of 5-10 μm;

0.00625 g of LFP with an average particle size of 15-20 μm, 0.015 g of LAG with an average particle size of 5-10 μm, and 0.00375 available from Timcal under the trade name Super P? A first anode 5 consisting of g carbon black. The mixture of ingredients was manually ground in agate induction for 20 minutes;

A 20 μm (stainless steel foil) current collector 6;

A second anode 7 identical to the first anode 5;

A solid electrolyte 8 consisting of 0.03 g of LAG with an average particle size of 5-10 μm;

A second negative electrode 9, which is identical to the first negative electrode 3; And

20 μm (copper foil) current collector 10.

Various components were placed in series in an 8 mm-diameter graphite die (grade 2333, Carbone Lorraine), inside the Papyex®. Protected with film. The die was then closed by a symmetric piston also made of grade 2333 graphite and introduced into the chamber of the SPS instrument used in Example 1, after which the chamber was pumped into secondary vacuum. The battery was formed under the conditions described in Example 1 above.

An 8 mm-diameter positive electrode cell with a total thickness of 1520 μm was obtained, which consisted of a 170 μm-thick composite positive electrode layer, a 200 μm-thick intermediate solid-electrolyte layer and a 370 μm-thick composite negative electrode layer.

Example 8 Preparation of a Stack of Two "All Solid" Li-Ion Batteries According to the Method of the Invention

In this example, an 8 mm-diameter battery was produced, where the anode / cathode mass ratio was 0.5 for an electrode composition comprising 25 wt% active electrode material, 60 wt% electrolyte and 15 wt% electron-conductive generating agent.

8 attached to the present specification shows a schematic diagram of a positive cell 11 comprising two batteries connected in series.

This serial stack (Figure 8) consists of:

20 μm (copper foil) current collector 12;

0.0125 g of LVP with an average particle size of 30-40 μm, 0.03 g of LAG with an average particle size of 5-10 μm, and 0.0075 g of Super P commercially available from Timcal with an average particle size of 50-100 nm. The first negative electrode 13 composed of carbon. The mixture of ingredients was manually ground in agate induction for 20 minutes;

A solid electrolyte 14 consisting of 0.03 g of LAG with an average particle size of 5-10 μm;

0.00625 g of LFP with an average particle size of 15-20 μm, 0.015 g of LAG with an average particle size of 5-10 μm, and 0.00375 available from Timcal under the trade name Super P? A first anode 15 composed of g carbon black. The mixture of ingredients was manually ground in agate induction for 20 minutes;

A 20 μm (stainless steel foil) current collector 16;

A second negative electrode 17 which is identical to the first negative electrode 13;

A solid electrolyte 18 consisting of 0.03 g of LAG with an average particle size of 5-10 μm;

A second anode 19 identical to the first anode 15; And

20 μm (stainless steel foil) current collector 20.

Various components were placed in series in an 8 mm-diameter graphite die (grade 2333, Carbone Lorraine), inside the Papyex®. Protected with film. The die was then closed by a symmetric piston also made of grade 2333 graphite and introduced into the chamber of the SPS instrument used in Example 1, after which the chamber was pumped into secondary vacuum. The battery was formed under the conditions described in Example 1 above.

A stack of two 8 mm-diameter series batteries having a total thickness of 1550 μm was obtained, the cell comprising a 170 μm-thick positive electrode composite layer, a 200 μm-thick intermediate solid-electrolyte layer and a 370 μm-thick layer of negative electrode composite It consists of.

Claims (32)

An all-solid-state lithium-ion battery having a monolithic body comprising at least one composite cathode layer and at least one composite anode layer, the layers separated from one another by at least one intermediate solid electrolyte layer As a manufacturing method of
Preparing a powdery mixture (MP1) comprising at least one active cathode material powder, at least one solid electrolyte powder and at least one electron-conductive generating agent; And
Preparing a powdered mixture (MP2) comprising at least one active lithium-based positive electrode material powder, at least one solid electrolyte powder and at least one electron-conductive generating agent;
The battery is formed in a single step by overlapping one or more mixture (MP1) layers and one or more mixture (MP2) layers, the layers being separated from each other by one or more intermediate solid electrolyte layers in powder form, and at the same time the 3 Sintered set of layers is sintered by pulse current at a pressure of 20 MPa or more,
The particle size of the solid electrolyte in powder form is 5 μm or less,
The contents of the solid electrolyte of each of the mixture (MP1) and the mixture (MP2) are independently of each other in the range of 10 to 80 wt%,
The content of the electron-conducting generating agent of each of the mixture (MP1) and the mixture (MP2) is independently from each other in the range of 2 to 25 wt%,
The content of the active electrode material of each of the mixture (MP1) and the mixture (MP2) is independently from each other in the range of 20 to 85 wt%. The method of claim 1,
The content of the solid-electrolyte of each of the mixture (MP1) and the mixture (MP2) is independently of each other in the range of 30 to 80 wt%. The method according to claim 1 or 2,
The particle size of the solid electrolyte powder which can be used in the mixture (MP1), the mixture (MP2) and the intermediate electrolyte layer is smaller than the particle size of the other powdery components present in the mixture (MP1) and the mixture (MP2). Method for producing a solid-state lithium-ion battery to be. 4. The method according to any one of claims 1 to 3,
Particle size of the solid electrolyte powder is a method for producing a solid-state lithium-ion battery, characterized in that less than 1 ㎛. 5. The method according to any one of claims 1 to 4,
Method for producing a solid-state lithium-ion battery, characterized in that the average particle size of the mixture (MP1) and the mixture (MP2) independently of each other in the range of 1 to 10㎛. The method according to any one of claims 1 to 5,
The particle size of the mixture (MP1) is substantially the same as the particle size of the mixture (MP2) method for producing a solid-state lithium-ion battery. 7. The method according to any one of claims 1 to 6,
The active cathode material is selected from lithium phosphate, titanium / lithium oxide, niobium phosphate, silicon and graphite and is optionally coated with a protective layer such as AlPO ₄ , Li ₂ SiO ₃ , ZrO ₂ , FePO ₄ . Method of manufacturing a normal type lithium-ion battery. The method of claim 7, wherein
The active cathode material is a lithium phosphate selected from Li ₃ V ₂ (PO ₄ ) ₃ , LiTi ₂ (PO ₄ ) ₃ or mixtures thereof. The method according to any one of claims 1 to 8,
The solid electrolyte is selected from lithium phosphates having the general formula Li _{1 + x} Al _x M _2-x (PO ₄ ) ₃ , wherein M = Ge, Ti, Zr, Hf and 0 <x <1 Method for producing an all-solid-state lithium-ion battery. 10. The method of claim 9,
Lithium phosphate is selected from Li _1.5 Al _0.5 Ge _1.5 (PO ₄ ) ₃ And Li _1.3 Al _0.3 Ti _1.7 (PO ₄ ) _{3 A} method for producing a solid-state lithium-ion battery, characterized in that. 11. The method according to any one of claims 1 to 10,
And said three layers comprise the same electrode. 11. The method according to any one of claims 1 to 10,
The solid electrolyte present in the mixture (MP1) is different from the solid electrolyte present in the mixture (MP2), the mixture (MP1) layer comprises at least one solid electrolyte (E1), and the mixture (MP2) layer is the solid At least one electrolyte (E1) comprising at least one solid electrolyte (E2) different from the electrolyte (E1), wherein the electrolyte layer separating the mixture (MP1) layer and the mixture (MP2) layer is in contact with the mixture (MP1) layer. A layer, and at least one electrolyte (E2) layer in contact with the mixture (MP2) layer, characterized in that the manufacturing method of the solid-state lithium-ion battery. 13. The method according to any one of claims 1 to 12,
The active cathode material is selected from lithium phosphate and lithium oxide, and is optionally coated with a protective layer such as AlPO ₄ , Li ₂ SiO ₃ , ZrO ₂ , FePO _4. . The method of claim 13,
The lithium phosphate which can be used as the active positive electrode material is an all-solid-state lithium-ion battery characterized in that it is selected from LiFePO ₄ , Li ₃ V ₂ (PO ₄ ) ₃ , LiCoPO ₄ , LiMnPO ₄ , LiNiPO ₄ and mixtures thereof. Manufacturing method. 15. The method according to any one of claims 1 to 14,
Wherein said active negative electrode material, at least one solid electrolyte and active positive electrode material are selected from lithium phosphate. 16. The method according to any one of claims 1 to 15,
Wherein said electron-conducting generator is selected from carbon-based materials, metals, and nitrides. 17. The method according to any one of claims 1 to 16,
The electron-conducting generator is a method for producing a solid-state lithium-ion battery, characterized in that the carbon-based material in the form of particles of a nano unit size. The method according to any one of claims 1 to 17,
The sintering operation is a method for producing a solid-state lithium-ion battery, characterized in that carried out under primary or secondary vacuum in an argon or nitrogen atmosphere. 19. The method according to any one of claims 1 to 18,
The sintering action is a method for producing a solid-state lithium-ion battery, characterized in that carried out at a pressure of 5 to 200 MPa. 20. The method according to any one of claims 1 to 19,
The maximum sintering temperature is a method for producing a solid-state lithium-ion battery, characterized in that in the range of 500 to 1000 ℃. 21. The method according to any one of claims 1 to 20,
Sintering action is 600 to 700 A process for producing a solid-state lithium-ion battery, characterized in that it is carried out under a secondary vacuum at a pressure of about 100 MPa at a maximum sintering temperature of &lt; RTI ID = 0.0 &gt; 22. The method according to any one of claims 1 to 21,
The magnitude of the pulse current is in the range of 10 to 8000 A, and the length of each pulse is in the range of 1 to 5 ms. The method according to any one of claims 1 to 22,
During battery formation, one or more current collectors are connected to the outer surface of the mixture (MP1) layer and / or the outer surface of the mixture (MP2) layer such that the mixture (MP1) layer, electrolyte layer and mixture (MP2) layer are sintered simultaneously. Method for producing a solid-state lithium-ion battery, characterized in that located. 24. The method of claim 23,
The current collector is selected from copper, nickel, stainless steel, aluminum, carbon, titanium, silver, gold, platinum or alloys thereof. The method of claim 23 or 24,
In order to simultaneously sinter five or more layers of the first collector / mixture (MP1) layer / solid electrolyte layer / mixture (MP2) layer / second collector, the first current collector is located in the mixture (MP1) layer and the second current collector Method for producing a solid-state lithium-ion battery, characterized in that located in the mixture (MP2) layer. An all-solid-state lithium-ion battery obtained by the manufacturing method according to any one of claims 1 to 25,
The battery comprises a monolithic body formed by three or more overlapping layers,
At least one composite cathode layer comprises at least one active cathode material, at least one solid electrolyte and at least one electron-conducting generator,
At least one composite anode layer comprises at least one active lithium-based anode material, at least one solid electrolyte and at least one electron-conducting generator,
At least one intermediate solid electrolyte layer separates the composite cathode layer and the composite anode layer,
The content of the solid electrolyte in each of the composite electrode layers is in a range from 10 to 80 wt% independently of each other,
The content of the electron-conducting generating agent of each of the composite electrode layers is independently in the range of 2 to 25 wt%,
The contents of the active cathode and anode materials of each of the composite electrode layers are independent of each other in the range of 20 to 85 wt%,
The thickness of each of said electrode layers is independently from each other in the range of from 30 to 1400 μm. The method of claim 26,
And the thickness of each of the composite electrode layers is independently from each other in the range of 50 μm to 800 μm. The method of claim 26 or 27,
The thickness of the intermediate electrolyte layer is a solid-state lithium-ion battery, characterized in that in the range of 10 to 500 ㎛. 29. The method according to any one of claims 26 to 28,
The solid electrolyte content of each of the composite electrode layers is independently in the range of 30 wt% to 80 wt%, all-solid-state lithium-ion battery. 30. The method according to any one of claims 26 to 29,
Wherein said monolithic body further comprises at least one current collector superimposed on the composite cathode layer and / or the composite anode layer on an outer side thereof. 31. The method of claim 30,
And the current collector layer is selected from copper, nickel, stainless steel, aluminum, carbon, titanium, silver, gold, platinum or alloys thereof. A battery stack comprising at least two batteries according to claim 30, wherein
Wherein the two or more batteries are connected by a current collector belonging to any one of the batteries, the current collector forming a physical barrier to the movement of ions.

Images